An electrochemical fuel cell having an anode, an ion transfer membrane and a cathode has liquid water delivered to the fluid flow channels within the cathode so as to maintain a relative humidity of 100% throughout the fluid flow channels. A calibration method and apparatus is described for determining an optimum quantity or range of quantities of liquid water to be delivered to the cathode fluid flow channels under varying operating conditions. An operating method and apparatus is described that ensures an optimum quantity of liquid water is delivered to the cathode fluid flow channels under varying operating conditions.
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1. A method of operating an electrochemical fuel cell stack comprising a plurality of fuel cells, each of the fuel cells comprising an anode, an ion transfer membrane, and a cathode, the method comprising:
delivering fluid fuel to one or more fluid flow channels in each anode of one or more fuel cells in the electrochemical fuel cell stack;
delivering fluid oxidant to one or more fluid flow channels in each cathode of the one or more fuel cells;
exhausting reaction by-products and unused oxidant from the one or more fluid flow channels in each cathode of the one or more fuel cells; and
delivering a sufficient quantity of liquid water to the one or more fluid flow channels in each cathode of the one or more fuel cells such that a relative humidity of 100% is maintained throughout the one or more fluid flow channels in each cathode of the one or more fuel cells;
wherein delivering the sufficient quantity of liquid water comprises:
determining, for each of a plurality of currents, a maximum voltage for the one or more fuel cells as a function of liquid water flow rate, the each of a plurality of currents being within a range of operating conditions of the one or more fuel cells;
determining a calibration function expressing a minimum liquid water flow rate as a function of current and/or air stoichiometry, the calibration function being determined by variation of water flow rate to the cathode operating at constant current and constant air stoichiometry to determine minimum and maximum water flow rates repeated for a plurality of stack currents or air stoichiometries; and
delivering at least the minimum liquid water flow rate for a corresponding current drawn from the one or more fuel cells and/or for the air stoichiometry, the delivered minimum liquid water flow rate being determined by the calibration function.
2. The method of
3. The method of
4. The method of
increasing a quantity of liquid water delivered to one or more fluid flow channels of each cathode of the one or more fuel cells as a function of fuel cell current in order to maintain a water factor greater than 1.0 for all currents within an operating range of the one or more fuel cells.
5. The method of
6. The method of
7. The method of
8. The method of
9. The method of
10. The method of
11. The method of
temporarily permitting delivery of a quantity of liquid water to one or more fluid flow channels of a cathode of the one or more fuel cells such that a relative humidity of less than 100% is maintained when an exhaust temperature of the cathode is below a predetermined threshold corresponding to a sub-optimal operating temperature.
13. The method of
14. The method of
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The present invention relates to electrochemical fuel cells, such as solid polymer electrolyte fuel cells, which convert fuel and oxidant into electrical energy and a reaction product.
A typical layout of a conventional fuel cell 10 is shown in
Sandwiching the polymer membrane and porous electrode layers is an anode fluid flow field plate 14 and a cathode fluid flow field plate 15. Intermediate backing layers 12a and 13a may also be employed between the anode fluid flow field plate 14 and the anode 12 and similarly between the cathode fluid flow field plate 15 and the cathode 13. The backing layers are of a porous nature and fabricated so as to ensure effective diffusion of gas to and from the anode and cathode surfaces as well as assisting in the management of water vapour and liquid water.
The fluid flow field plates 14, 15 are formed from an electrically conductive, non-porous material by which electrical contact can be made to the respective anode electrode 12 or cathode electrode 13. At the same time, the fluid flow field plates must facilitate the delivery and/or exhaust of fluid fuel, oxidant and/or reaction product to or from the porous electrodes. This is conventionally effected by forming fluid flow passages in a surface of the fluid flow field plates, such as grooves or channels 16 in the surface presented to the porous electrodes 12, 13.
With reference also to
Other manifold apertures 23, 25 may be provided for fuel, oxidant, other fluids or exhaust communication to other channels in the plates, not shown.
The channels 16 in the fluid flow field plates 14, 15 may be open ended at both ends, ie. the channels extending between an inlet manifold 21 and an outlet manifold 22 as shown, allowing a continuous throughput of fluid, typically used for a combined oxidant supply and reactant exhaust. Alternatively, the channels 16 may be closed at one end, ie. each channel has communication with only an input manifold 21 to supply fluid, relying entirely on 100% transfer of gaseous material into and out of the porous electrodes of the MEA. The closed channel may typically be used to deliver hydrogen fuel to the MEA 11-13 in a comb type structure.
With reference to
In order to obtain high and sustained power delivery capability from a fuel cell, it is generally necessary to maintain a high water content within the membrane-electrode assembly, and in particular within the membrane.
In the prior art, this is conventionally achieved by humidifying the feed gases, either fuel, air or both, fed via manifolds 21, 22 or 23 and channels 16. In other words, water in the vapour phase (hereinafter ‘gaseous water’) is introduced into the channels 16. This also can also contribute, to some limited extent, to heat management within the fuel cell assembly.
Another method is to deliver water in the liquid phase (hereinafter ‘liquid water’) directly to the membrane 11, 34, e.g. directly to the electrode surfaces or into the channels 16 of the bipolar plates 31. This technique has the advantage of not only supplying the water to maintain a high membrane water content but can also act to cool significantly the fuel cell through evaporation and extraction of latent heat of vaporisation. A detailed description of techniques for introducing liquid phase water directly to the electrode surfaces or into the channels 16 has been described in international patent application no. PCT/GB03/02973 (unpublished at the time of filing this application). Relevant parts of that document are therefore reproduced herein where appropriate.
This direct heat removal process that provides for the extraction of thermal energy via the exit gas stream has distinct advantages associated with the elimination of intermediate cooling plates within the fuel cell stack assembly.
It is an object of the present invention to provide a method and apparatus for providing improved operation of an evaporatively cooled fuel cell stack through introduction of excess water into the channels 16 of the cathode electrode.
According to one aspect, the present invention provides a method of operating an electrochemical fuel cell having an anode, an ion transfer membrane and a cathode, comprising the steps of:
According to another aspect, the present invention provides an electrochemical fuel cell assembly comprising:
Embodiments of the present invention will now be described by way of example and with reference to the accompanying drawings in which:
During operation of a fuel cell stack assembly 30, heat is generated within the fuel cell stack as a consequence of electrochemical and electrical losses. In an example of an evaporatively cooled fuel cell 10 in a stack assembly, shown schematically in
Evaporation of liquid water 104 will occur if the partial pressure of gaseous water in the cathode air stream is low enough, i.e. at conditions of relative humidity<100%, and there is a supply of heat to vaporise the liquid water. Once the local conditions are such that the relative humidity of water is 100%, i.e. the air is saturated with water vapour, no further evaporation will occur unless any of the following three conditions prevail: (i) the air flow rate is increased such that the partial pressure of gaseous water is lowered in inverse proportion; (ii) the total pressure is lowered such that the partial pressure of gaseous water is lowered proportionally; and (iii) the local temperature increases such that the equilibrium point is shifted whereby more evaporation may occur until the air becomes fully saturated.
Therefore, for a fuel cell 10 operating with excess water at the cathode 13 at each location in the fuel cell stack 30, at constant pressure and with a constant cathode air flow rate, the local equilibrium conditions are such that the air is fully saturated and any further heat removal through evaporation can only be effected by an increase in local temperature.
The actual increase in temperature to effect evaporation, and therefore cooling, depends on the sensitivity of the equilibrium point for evaporation at the prevailing conditions and the degree of cooling required.
As shown in
Additionally, the presence of excess water within individual channels 16 or passages in the fuel cell stack assembly 30 gives rise to implicit control of the air flow rate within each channel as follows. If a given passage has a higher than average air flow rate, then additional water can be evaporated into the air flow to provide additional cooling if required. This leads to a higher than average volume flow rate at exit from the flow passage which, in the presence of a uniform pressure drop across all flow passages, limits the air flow rate into the cell passage providing implicit regulation of the air flow leading to improved stack thermal balance and hence improved stack cell voltage balance. A uniform pressure drop across all channels 16 is generally provided by the relative dimensions of the manifolds 21, 22 and the channels 16.
Explicit control of the stack temperature can be achieved if required through moderation of the cathode air flow rate and/or through modification of the total pressure of the cathode air stream. In other words, the air flow rate can be increased, thereby lowering the partial pressure of water vapour, by increasing the volume of air into which the water can vaporise. Therefore, additional water can be vaporised before saturation occurs, creating additional cooling and resulting in a lower stack operating temperature.
Alternatively, or in addition, the outlet pressure can be reduced. This will again lower the partial pressure of water vapour, by lowering the total pressure. This has the effect of shifting the equilibrium point such that additional water can be vaporised before saturation is reached, creating additional cooling and resulting in a lower stack operating temperature.
Other factors, such as the anode flow rate, fuel and oxidant input temperature, surface losses etc., are found to be less significant.
In a preferred embodiment of a predominantly unpressurised system, the typical operating temperature of the fuel cell stack is in the range 70 to 80 degrees C. However, in principle, this value can be varied in the range 65 to 95 degrees C. through adjustment of the air flow rate and/or total pressure of the cathode air stream. At low power levels, where evaporative cooling is not dominant, the operating temperature of the stack can be significantly cooler. Operating the system at higher or lower pressures will enable significant variation in the temperature ranges quoted above.
In practice, the average temperature of the reactants and liquid water supplied to the fuel cell stack can be lower than the stack operating temperature. Therefore, some cooling will be provided by the heating of these input flows to the stack operating temperature. Once the input flows have reached the stack operating temperature, the remainder of the cooling will be provided by evaporation of the liquid water into the cathode air stream. The proportion of evaporative cooling is dependent on a number of factors including the cathode air flow rate, the water flow rate, the fuel cell stack power and the temperature of the inlet flows. In most cases, evaporative cooling is the dominant cooling mechanism leading to a high degree of implicit temperature control as previously explained. However, for cases where the average temperature of the inlet flows is lower than the stack operating temperature, there will be a temperature gradient in the stack in the region where the reactants and liquid water are input.
For evaporative cooling to be effective, there must be sufficient liquid water present at each part of the fuel cell stack. If insufficient water is present then the performance of the stack will be reduced with potentially serious consequences.
Possible problems include: (i) drying of the membrane, leading to a lower voltage across the relevant cell; and (ii) hotspots caused by the absence of liquid water and hence lack of evaporative cooling, leading to deterioration of the membrane and a reduction in life.
In order to ensure that sufficient liquid water is present to effect cooling through evaporation, alternative strategies can be adopted: (i) precise metering of liquid water to the cathode such that there is exactly enough water to maintain a relative humidity of 100% across the entire surface of the cathode and in each cell of the fuel cell stack; or (ii) over-supply of liquid water to the entire stack such that there is always excess water present across the entire surface of the cathode and in each cell of the fuel cell stack. To achieve adequate delivery of liquid water to the cathode, water injection points may be provided for each and every cathode channel 16 as will be illustrated later.
In practical fuel cells, the precise metering of liquid water to each part of the fuel cell stack is difficult to achieve. Additionally, manufacturing tolerances and non-uniform operating conditions lead to differing requirements for cooling at each location in the fuel cell stack thereby exacerbating the difficulties associated with precise metering.
Therefore, the over-supply of liquid water to the cathode such that there is always excess liquid water present at the cathode at each location within the stack is the preferred method since this ensures that drying of the membrane and hotspots are avoided, leading to improved stack performance and life.
Thus, in one general aspect, the supply of excess liquid water to the cathode ensures that a relative humidity of 100% is maintained substantially throughout the fluid flow channels in the cathode.
In another aspect, the fuel cell is operated such that, for any measured cell power delivery, liquid water injection rate into the cathode and/or gas flow through the cathode are controlled to ensure that there is more liquid water at all regions of the cathode surface than can be evaporated in the prevailing temperature and pressure conditions.
In another aspect, the above conditions are applied to a plurality of such cells in a fuel cell stack having a common oxidant supply manifold and a common water injection manifold such that, for any measured stack power delivery, liquid water injection rate into the water injection manifold and/or gas flow rate in the oxidant supply manifold are controlled to ensure that there is more liquid water at all regions of the cathode surfaces of all cells than can be evaporated in the prevailing temperature and pressure conditions.
For a practical stack subject to real non-uniformities and under normal operating conditions with a water factor of less than unity, it will be appreciated that some parts of the stack could be receiving less liquid water than is required to maintain a relative humidity of 100% substantially throughout the fluid flow channels in the cathode. Correspondingly, there may be some parts of the stack which are receiving more liquid water than is required to maintain a relative humidity of 100% substantially throughout the fluid flow channels in the cathode. Therefore, in another aspect of the invention, the supply of excess liquid water to the stack is selected such that all parts of the stack will receive at least the minimum amount of liquid water required to maintain a relative humidity of 100% substantially throughout the fluid flow channels in the cathode, corresponding to a water factor of greater than unity for the stack.
Also at higher flow rates, the cell balance (as indicated by cell voltage monitoring) can deteriorate indicating an upper limit to the maximum water factor that can be used for the stack. It is also possible that the maximum water flow rate may be set by the maximum achievable using a suitable water pump.
Despite these limiting effects, it has been determined that a large operating window can be defined where significant amounts of excess water can be supplied to the cathode ensuring adequate hydration and cooling of each part of the fuel cell stack.
It is helpful to describe the quantity of water delivered to the cathode as a multiple of the theoretical minimum amount required for evaporative cooling, i.e. a ‘water factor’ WF is hereby defined in which:
WF=mw/mw(minimum)
where mw is the mass flow rate of liquid water delivered, and mw(minimum) is the theoretical minimum mass flow rate of liquid water as calculated below.
The theoretical minimum amount of water required for evaporative cooling can be calculated by performing a heat balance on the fuel cell and assuming that:
(i) the enthalpy of reaction is equal to the lower heating value of the fuel, since gaseous water is produced as a product (in the absence of excess water);
(ii) the heat load on the fuel cell is derived from an experimental value of fuel cell stack efficiency as a function of stack current;
(iii) the heat load is equal to the thermal enthalpy rise of the products over the reactants including complete evaporation of liquid water supplied to the cathode.
The actual water factor for a given operating point can therefore be defined as a multiple of this value.
It will be appreciated that the water factor could be defined in other ways than the definition given above, which could result in slightly different preferred ranges of values of water factor, according to the definition used.
As discussed, stack non-uniformities and the effect of these on water flow rate for optimum performance (as shown between lines 121 and 122 of
The upper and lower limits 130, 131 of water factor may be determined via testing or calibration of the relevant fuel cell stack 30. Calibration of a stack can be achieved through variation of the water flow rate to the cathode operating at constant current and constant air stoichiometry to determine the minimum water flow rates indicated by line 121 and the maximum water flow rates indicated by line 122. This calibration is repeated for a range of possible stack currents (and possibly also for a range of allowable air stoichiometries) that will correspond to a normal range of operating conditions of the stack. Thus, the calibration defines upper and lower limits of water factor as a function of stack current.
The expression ‘air stoichiometry’ as used herein refers to the amount of oxygen supplied at the input 103 normalised by the amount of oxygen consumed in the electrochemical reaction. Thus, for an air stoichiometry of 1, all of the oxygen in the air is combined with hydrogen to form water. For a stoichiometry of 2, 50% of the oxygen is consumed in the cell 10 and 50% is present in the cathode exhaust 101. The amount of oxygen required for the reaction is a direct function of stack power, stack efficiency and the energy change associated with the reaction.
In a mass manufacturing environment, it is also possible to test a number of representative stacks in order that a single set of limits with suitable error margins may be determined that will be acceptable for all stacks of a given configuration.
In a preferred embodiment, the cathode air flow rate 103 is adjusted in proportion to the stack current such that the stack operates with an air stoichiometry of approximately 2, set by electrochemical requirements. In practice, however, the cathode air flow rate can be varied such that the air stoichiometry is within the range 1.1 to 10, and more preferably within the range 1.4 to 4, depending on the precise requirements of the fuel cell stack. At low currents, and hence low consumption of reactants in the cell, the air stoichiometry can be significantly higher than these values, since the minimum air flow rate is limited by the minimum flow rate delivery of the air compressor.
In a preferred embodiment, the water flow rate is set to be a linear function of stack current as shown schematically in
In practice, the water factor can be set anywhere in the range 0 to 40 depending on the operating conditions of the stack and the acceptable maximum drop-off in stack performance as a consequence of excess water (refer to
Monitoring of the cathode exhaust temperature can be used to indicate the stack operating temperature and provide feedback control for the water feed pump. Thus, in one aspect, the system may temporarily permit delivery of a quantity of liquid water to the fluid flow channels within the cathode such that a relative humidity of less than 100% (water factor<1) is maintained when the cathode exhaust temperature is below a predetermined threshold corresponding to a sub-optimal operating temperature, or for a predetermined period following cold start of the fuel cell.
A metering pump, flow controller or a pressure control method can be used to regulate the water feed rate. At low power levels, the amount of water required might be lower than the minimum flow rate obtainable with the water pump. Therefore, at low power levels a minimum water flow rate could be set corresponding to the minimum voltage set point for the water pump to prevent the pump from stalling. This is shown schematically in
It will be appreciated that the amount of water delivered to the fuel cell stack can, in principle, follow any function of current provided that the flow rate lies within the minimum and maximum levels of water factor determined by calibration of the relevant fuel cell stack or of a number of representative fuel cell stacks.
Once a water factor control strategy has been defined, additional flexibility in cooling can be achieved through adjustment of the cathode air flow rate and/or cathode air total pressure.
Additionally, the stack can be equipped with cell voltage monitoring capability such that the operational voltage is used as an indicator of insufficient or excess water, the necessary adjustments being made in real time.
An exemplary arrangement for implementing water management in a fuel cell stack is now described in connection with
A fuel cell system 140 includes a fuel cell stack 30 having a fuel input line 102, an anode exhaust line 100, an air feed line 103, a water injection line 104 and a cathode exhaust line 101. The fuel input line is fed from a fuel source 141, possibly via a humidifier 142 according to well known principles. The anode exhaust line 100 may be fed directly to ambient 143, or may be at least partially recycled according to known principles using a recycle control loop 144. The air feed line 103 is fed by an air compressor 145. The water injection line 104 is supplied by a water pump 146. Water can be supplied from an appropriate purified water supply or recycled from the cathode exhaust by way of a suitable condenser (not shown). The cathode exhaust line 101 may be directed to ambient, and preferably includes an exhaust sensor 147 which senses at least exhaust temperature.
The cathode exhaust may include a pump 148 for reducing and/or controlling the cathode exhaust pressure. The pump 148 may be in addition to, or instead of, a pumped air supply from compressor 145, i.e. the air supply could otherwise be at ambient pressure.
Also included within the fuel cell system 140 is a controller 150 which preferably receives sensor inputs corresponding to stack voltage 151, stack current 152 and exhaust temperature 153. The controller 150 is also coupled to the air compressor 145 and water injection pump 146 by way of suitable control lines.
The controller 150 may be configured to operate in two possible modes.
In a first mode, the controller 150 may be adapted to obtain calibration data for subsequent operation of the fuel cell stack 30. In a calibration mode, the controller 150 varies water flow supplied by the water injection pump 146 under conditions of constant input air pressure and constant current drawn from the fuel cell stack, and receives sensed voltage levels of the stack to thereby determine appropriate maximum and minimum water factors 121, 122 (
In a second mode, the controller 150 is adapted to use the calibration data stored in calibration table 154 in order to maintain optimum running conditions of the fuel cell stack. For example, the controller 150 is adapted to monitor stack voltage and current, and to control the water injection pump 146 (and possibly also the inlet air compressor) to maintain an appropriate water factor for optimum performance of the fuel cell. In preferred arrangements, this water factor lies in the range 1.5 to 40, and more preferably in the range 3 to 6.
As previously described, the controller may also monitor cathode exhaust temperature by way of sensor 147, and deliver a smaller quantity of water when the cathode exhaust temperature is below a predetermined threshold corresponding to a sub-optimal operating temperature, e.g. during start up of the fuel cell. In another example, this ‘warm-up’ phase could be controlled by a timer rather than by exhaust temperature.
In the exemplary embodiment of
Although the exemplary embodiment of
A number of mechanisms are possible for delivering liquid water in precisely controlled quantities to fluid flow channels in the cathode fluid flow field plates. Exemplary mechanisms are described in PCT/GB03/02973 (unpublished at the time of filing this application), details of which are described hereinafter with reference to
With reference to
In a preferred arrangement, the laminated structure is provided in the form of two foil layers 41, 42 overlying the plate 40, the position of which foils are shown in dashed outline in
In the preferred embodiment as illustrated, the convergence structures 54 comprise arcuate recesses 55 cut into the second edge 45 of the foil 41 at water injection points 49 adapted to be coincident with predetermined positions over channels 16, shown in outline on the figure.
The pressure distribution gallery 52 preferably comprises an array of intercommunicating channels 56 which baffle the incoming water from the first series of channels 51 and effectively distribute it along the entire length of the foil 41 so that each group of the second series of channels 53 receives water at a substantially similar pressure.
Referring back to
It is noted that the foil layers are very thin compared with the plate 40 thickness, the thickness of the foil layers being easily absorbed by the MEA 34 and any gaskets interposed between the plates. The components in
It will be recognised that the water distribution channels 51, 52, 53 need not be formed in the lower foil 41. In another embodiment, shown in
In the
As indicated above, the lower (cover) foil 81 provides a closure to the channels 80 forming a barrier preventing water from escaping into underlying channels 16 in the fluid flow plate 40 in the wrong places, eg. where the water injection conduits traverse the fuel and/or oxidant channels 16 (eg. at location 85).
Preferably, the foils as described above are formed from a metal, such as stainless steel. However, any suitable material having appropriate pressurised water containment properties could be used, and the expression “foil” used throughout the present specification is to be construed accordingly. Preferably, the foils are electrically conductive but they need not be so, since they do not impinge on the active area of the MEA.
In a preferred embodiment, the fluid flow channels 16 in the anode or cathode plates 40 are typically between 0.4 mm and 1.2 mm in width and depth. It is found that a channel width and depth of 10 microns, chemically etched into the water distribution foil, serves to provide the necessary degree of water injection.
In use, the pressure of water being delivered via manifold 25 is controlled to ensure a significant pressure difference between the water supply and the gas pressure in the fluid flow channels 16, achieving an equal distribution of water between the thousands of flow paths. In the preferred embodiment, water is delivered to the manifold at a gauge pressure in the range 0.5-3 bar H2O.
An advantage of this approach is that the water distribution membrane is extremely thin and can easily be located within the available space within bipolar plates or in the gasket area.
The volumetric water dispensing accuracy can also be very precisely controlled by suitable design of the water injection conduit pattern and channel dimensions.
As illustrated in
An advantage of water injection into the exit tracks is a reduction of pressure drop in reactant gas flows. This is because the water does not pass through the diffusion medium causing masking of void space for the gas passage. Similarly the elimination of water flow through the diffusion medium will also reduce the attrition of the medium and its gradual fragmentation and structural deterioration.
The evaporative cooling process is effective in the exit tracks and water content of the membrane is maintained due to saturation of the air with water vapour.
Other embodiments are intentionally within the scope of the accompanying claims.
Hood, Peter David, Foster, Simon Edward, Grange, Nathan, Cole, Jonathan, Baird, Scott, Matcham, Jeremy Stephen, Kells, Ashley, Adcock, Paul L., Benson, Paul Alan
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